JP2911911B2 - Epoxy compound polymerization method - Google Patents
Epoxy compound polymerization methodInfo
- Publication number
- JP2911911B2 JP2911911B2 JP1102375A JP10237589A JP2911911B2 JP 2911911 B2 JP2911911 B2 JP 2911911B2 JP 1102375 A JP1102375 A JP 1102375A JP 10237589 A JP10237589 A JP 10237589A JP 2911911 B2 JP2911911 B2 JP 2911911B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- epoxy compound
- mmol
- reaction
- polyether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、エポキシ化合物の重合方法に関するもので
ある。The present invention relates to a method for polymerizing an epoxy compound.
エポキシ化合物の開環重合により得られるポリエーテ
ルは、特殊ゴム、界面活性剤など用途は広い。Polyethers obtained by ring-opening polymerization of epoxy compounds have a wide range of uses such as special rubbers and surfactants.
重合反応の進歩に伴って、分子量および分子量分布、
共重合体の連鎖分布、末端基の規制など構造の規制され
たポリマーの合成も可能となり、新しい機能性高分子へ
の展開がなされ、ポリエーテルにおいても同様の試みが
なされている。With the progress of polymerization reaction, molecular weight and molecular weight distribution,
It is also possible to synthesize a polymer whose structure is regulated, such as the chain distribution of the copolymer and the terminal groups, which has been developed into a new functional polymer, and similar attempts have been made for polyethers.
ところで、エポキシ化合物のカチオン触媒による重合
では、低分子量のポリマーしか得られず、また副反応も
多い。アルカリ触媒によるエチレンオキシドのアニオン
重合は、リビング重合機構で進行し、単分散性のポリエ
ーテルが得られるが、モノマーが限定される嫌いがあ
る。他方、配位アニオン重合により、高分子量のポリエ
ーテルが容易に得られるが、分子量および分布の規制は
困難である。By the way, in the polymerization of an epoxy compound with a cationic catalyst, only a low molecular weight polymer can be obtained, and there are many side reactions. The anionic polymerization of ethylene oxide by an alkali catalyst proceeds by a living polymerization mechanism, and a monodisperse polyether is obtained. On the other hand, high molecular weight polyethers can be easily obtained by coordination anionic polymerization, but it is difficult to regulate molecular weight and distribution.
井上らは、アルミニウムポルフィン錯体が、エポキシ
化合物のリビング重合に極めて有効な開始剤になること
を報告している［S.Inoue,T.Aida,Macromol.Chem.Macro
mol.Symp.,6,217（1986）］。Inoue et al. Report that aluminum porphine complexes are extremely effective initiators for living polymerization of epoxy compounds [S. Inoue, T. Aida, Macromol . Chem. Macro.
mol. Symp., 6 , 217 (1986)].
一方、ウェブスターらは、シリルケテンアセタールに
よるグループトランスファー重合で、メタクリル酸エス
テルの単分散ポリマーを得ているが［D.Y.Sogah,W.R.He
rtler,O.W.Webster,G.M.Cohen,Macromolecules.,20,147
3（1987）］、その開環重合例はない。On the other hand, Webster et al. Obtained a monodisperse polymer of methacrylate by group transfer polymerization using silyl ketene acetal [DYSogah, WRHe
rtler, OWWebster, GMCohen, Macromolecules. , 20,147
3 (1987)], there is no ring-opening polymerization example.
本発明者らは既にCaFを触媒として、アリールシリル
エーテルによるグリシジルエーテル型エポキシド類の環
開反応が進行し、高収率で位置選択的な付加生成物が得
られることを見出している（特願昭63−57981号）。The present inventors have already found that the ring-opening reaction of glycidyl ether type epoxides with arylsilyl ethers proceeds using CaF as a catalyst, and regioselective addition products can be obtained in high yield (Japanese Patent Application 63-57981).
〔課題を解決するための手段〕 本発明者らは、CsFを触媒とするシリルエーテルとア
ルキルグリシジルエーテルとの反応においては、アリー
ルグリシジルエーテルとの反応の場合と異なり、付加生
成物はさらに過剰のグリシジルエーテルと反応すること
を新たに見出し、本反応を応用して構造規制を高度に可
能とするエポキシ化合物の新規な重合方法の発明に到達
した。 [Means for Solving the Problems] In the reaction of silyl ether with alkyl glycidyl ether catalyzed by CsF, unlike the reaction with aryl glycidyl ether, the addition product is further excessive. They have newly found that they react with glycidyl ether, and have arrived at the invention of a novel polymerization method of an epoxy compound which enables a high degree of structural regulation by applying this reaction.
即ち、本発明のエポキシ化合物の重合方法は、一般式
（Ｉ） （式中Ｒは置換又は無置換のアルキル基を示す） で示されるエポキシ化合物を、一般式（II） （式中、R1,R2,R3はそれぞれ置換又は無置換のアルキル
基またはアリール基を示す） で示されるシリルエーテル0.01〜0.2当量を開始剤とし
て、CsFの存在下に重合させ、末端にシリルオキシ基を
持つポリエーテルを得ることを特徴とする。That is, the method for polymerizing the epoxy compound of the present invention is represented by the general formula (I): (Wherein R represents a substituted or unsubstituted alkyl group) represented by the general formula (II) (Wherein R 1 , R 2 , and R 3 each represent a substituted or unsubstituted alkyl group or an aryl group). The initiator is polymerized in the presence of CsF, using 0.01 to 0.2 equivalents of a silyl ether represented by the following formula: To obtain a polyether having a silyloxy group.
一般式（Ｉ）で示されるエポキシ化合物としては、Ｒ
が炭素原子数１〜20のアルキル基、ハロゲン置換アルキ
ル基、またはオレフィン、ニトリル、エステル、アミ
ド、アミンエーテルなどの置換基を持つアルキル基を有
するグリシジルエーテルが挙げられ、好ましくはＲとし
て炭素原子数１〜４の直鎖もしくは分岐型アルキル基を
持つグリシジルエーテルが挙げられる。The epoxy compound represented by the general formula (I) includes R
Is a glycidyl ether having an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group, or an alkyl group having a substituent such as an olefin, a nitrile, an ester, an amide, or an amine ether. Glycidyl ethers having 1 to 4 linear or branched alkyl groups are exemplified.
一般式（II）で示されるシリルエーテルとしては、
R1,R2,R3が炭素原子数１〜20のアルキル基、アリール
基、もしくはアリールカルボニルオキシ、アルキル、ビ
ニル、ハロゲン、シアノ、カルバモイル置換アリール基
のものが挙げられ、好ましくは、無置換またはアルキル
置換フェニルトリアルキルシリルエーテルが挙げられ
る。As the silyl ether represented by the general formula (II),
R 1 , R 2 , and R 3 each have an alkyl group having 1 to 20 carbon atoms, an aryl group, or an arylcarbonyloxy, alkyl, vinyl, halogen, cyano, or carbamoyl-substituted aryl group, and are preferably unsubstituted Or an alkyl-substituted phenyltrialkylsilyl ether.
本発明のシリルエーテル化合物開始剤の使用量は、一
般式（Ｉ）のエポキシ化合物に対して、0.001〜0.5当
量、好ましくは0.01〜0.2当量程度が好ましい。The amount of the silyl ether compound initiator of the present invention to be used is preferably about 0.001 to 0.5 equivalent, more preferably about 0.01 to 0.2 equivalent based on the epoxy compound of the general formula (I).
本発明で用いられる無機フッ化物触媒としては、アル
カリ金属のフッ化物が挙げられ、例えばCsF、KFなどが
ある。Examples of the inorganic fluoride catalyst used in the present invention include alkali metal fluorides, such as CsF and KF.
無機フッ化物触媒の使用量は、一般式（Ｉ）のエポキ
シ化合物に対して、0.001〜0.05当量が好ましく、さら
に好ましくは0.005〜0.02当量である。The amount of the inorganic fluoride catalyst to be used is preferably 0.001 to 0.05 equivalent, more preferably 0.005 to 0.02 equivalent to the epoxy compound of the general formula (I).
本発明の重合反応は、無溶媒中もしくは非プロトン性
有機溶媒中で行うことができる。非プロトン性有機溶媒
としては、アセトニトリル、アセトン、DMF、THFなどが
挙げられる。非プロトン性有機溶媒の使用量は、一般式
（Ｉ）のエポキシ化合物に対して0.3〜２当量程度が好
ましい。The polymerization reaction of the present invention can be carried out without a solvent or in an aprotic organic solvent. Examples of the aprotic organic solvent include acetonitrile, acetone, DMF, THF and the like. The use amount of the aprotic organic solvent is preferably about 0.3 to 2 equivalents to the epoxy compound of the general formula (I).
本発明の重合反応は、脱気封管中、100〜200℃で、１
分〜10時間行うことができる。The polymerization reaction of the present invention is carried out in a degassed sealed tube at 100 to 200 ° C for 1 hour.
Can be performed for minutes to 10 hours.
本発明の好ましい実施態様を次に述べる。 Preferred embodiments of the present invention are described below.
アルキルグリシジルエーテルを無溶媒下、0.01〜0.2
当量の置換フェニルトリメチルシリルエーテルを開始剤
とし、0.005〜0.02当量のCsF触媒を用い、脱気封管中、
115〜150℃で、５分〜２時間重合させる。Alkyl glycidyl ether without solvent, 0.01-0.2
Using an equivalent of substituted phenyltrimethylsilyl ether as an initiator, using 0.005 to 0.02 equivalent of CsF catalyst, in a degassed sealed tube,
Polymerize at 115-150 ° C for 5 minutes to 2 hours.
反応後触媒を濾別し、未反応のグリシジルエーテルを
減圧除去すると次式の単分散性の高いポリエーテルまた
はオリゴエーテルが得られる。After the reaction, the catalyst is filtered off and unreacted glycidyl ether is removed under reduced pressure to obtain a polyether or oligoether having the following formula and high monodispersity.
〔発明の効果〕 本発明は、グリシジルエーテル型のエポキシ化合物を
新規重合方法で重合させるものである。 [Effect of the Invention] The present invention is to polymerize a glycidyl ether type epoxy compound by a novel polymerization method.
本発明によれば、酸・塩基を用いることなく、しかも
短時間で重合が進行し、単分散性の高いポリエーテルが
得られる。エポキシ化合物と開始剤のモル比を変化させ
れば容易に分子量も制御でき、オリゴマーも得られる。
さらにブロック共重合体、星型ポリマーの合成への展開
も可能で可能である。しかも本発明の重合反応は選択性
も高く、種々の機能団を持つポリエーテルの製造、新規
マクロマーの開発に応用できる。According to the present invention, the polymerization proceeds in a short time without using an acid or a base, and a polyether having high monodispersity can be obtained. By changing the molar ratio between the epoxy compound and the initiator, the molecular weight can be easily controlled, and an oligomer can be obtained.
Further, it can be applied to the synthesis of block copolymers and star polymers. Moreover, the polymerization reaction of the present invention has high selectivity and can be applied to the production of polyethers having various functional groups and the development of new macromers.
本発明の重合系は100℃以上の加熱を必要とすること
から、エポキシ化合物に対する熱潜在性重合開始剤とし
ても利用できる。Since the polymerization system of the present invention requires heating at 100 ° C. or higher, it can also be used as a thermal latent polymerization initiator for epoxy compounds.
以下、実施例により本発明を更に詳細に説明するが、
本発明はこれらの実施例に限定されるものではない。Hereinafter, the present invention will be described in more detail by examples,
The present invention is not limited to these examples.
実施例１ 重合管に、CsF 260mg（1.71ミリモル）を量り込み、
加熱乾燥した後、ｎ−ブチルグリシジルエーテル12.2ml
（85.6ミリモル）、およびフェニルトリメチルシリルエ
ーテル0.31ml（1.71ミリモル）を加え、脱気封管後、13
0℃で15分間重合させた。反応後、反応液を濾過し、CsF
を除き、さらに未反応のグリシジルエーテルを減圧除去
すると、ポリエーテル9.2g（収率82％）が得られた。Example 1 260 mg (1.71 mmol) of CsF was weighed into a polymerization tube,
After heating and drying, n-butyl glycidyl ether 12.2 ml
(85.6 mmol), and 0.31 ml (1.71 mmol) of phenyltrimethylsilyl ether were added.
Polymerization was carried out at 0 ° C. for 15 minutes. After the reaction, the reaction solution is filtered, and CsF
Then, unreacted glycidyl ether was removed under reduced pressure to obtain 9.2 g (yield: 82%) of polyether.
IR及び1H−NMR分析の結果から、末端にフェノキシ
基、およびトリメチルシリルオキシ基を持つ次の構造の
ポリエーテルであることを確認した。From the results of IR and 1 H-NMR analysis, it was confirmed that the polyether had the following structure having a phenoxy group and a trimethylsilyloxy group at the terminal.
またGPC分析〔溶媒：テトラヒドロフラン、分子量
（ポリスチレン換算）：ｎ＝5310（計算値:5490）、
分子量分布（Ｄ＝w/ｎ）＝1.17〕の結果から、本発
明の重合方法が単分散性の高いポリエーテルを与えるこ
とが判明した。 GPC analysis [solvent: tetrahydrofuran, molecular weight (polystyrene conversion): n = 5310 (calculated value: 5490),
From the result of the molecular weight distribution (D = w / n) = 1.17], it was found that the polymerization method of the present invention gave a polyether having high monodispersity.
実施例２〜４ 重合管に、CsF 130mg（0.85ミリモル）を量り込み、
加熱乾燥した後、ｎ−ブチルグリシジルエーテル12.2ml
（85.6ミリモル）、およびフェニルトリメチルシリルエ
ーテル0.31ml（1.71ミリモル）を加え、実施例１と同様
にして、115℃で15,40,及び80分間それぞれ反応させ、
ポリエーテルを得た。Examples 2 to 4 130 mg (0.85 mmol) of CsF was weighed into a polymerization tube.
After heating and drying, n-butyl glycidyl ether 12.2 ml
(85.6 mmol), and 0.31 ml (1.71 mmol) of phenyltrimethylsilyl ether were added, and reacted at 115 ° C. for 15, 40, and 80 minutes, respectively, in the same manner as in Example 1.
A polyether was obtained.
第１図に実施例２〜４における生成物のGPCチャート
を示した。本発明の重合系により単分散性の高いポリマ
ーが得られ、重合度の上昇につれ、分子量が増加してい
ることが明らかである。FIG. 1 shows GPC charts of the products in Examples 2 to 4. It is apparent that a polymer having high monodispersity can be obtained by the polymerization system of the present invention, and that the molecular weight increases as the degree of polymerization increases.
実施例５ 重合管に、CsF 130mg（0.856ミリモル）を量り込み、
加熱乾燥した後、ｎ−ブチルグリシジルエーテル12.2ml
（85.6ミリモル）、およびフェニルトリメチルシリルエ
ーテル1.56ml（8.56ミリモル）を加え、実施例１と同様
にして、130℃で30分間反応させ、ポリエーテル6.70g
（収率60％）を得た。Example 5 130 mg (0.856 mmol) of CsF was weighed into a polymerization tube,
After heating and drying, n-butyl glycidyl ether 12.2 ml
(85.6 mmol) and 1.56 ml (8.56 mmol) of phenyltrimethylsilyl ether, and reacted at 130 ° C. for 30 minutes in the same manner as in Example 1 to obtain 6.70 g of polyether.
(60% yield).
実施例６ 重合管に、CaF 260mg（1.7ミリモル）を量り込み、加
熱乾燥した後、メチルグリシジルエーテル7.7ml（85.6
ミリモル）、およびフェニルトリメチルシリルエーテル
0.31ml（1.7ミリモル）を加え、実施例１と同様にし
て、130℃で30分間反応させ、ポリエーテル7.5g（収率1
00％）を得た。ｎ＝2440;D＝1.23 比較例１ 本発明の開始剤と無機フッ化物触媒の代わりに、セシ
ウムフェノレート（PhOCs）を用いる他は実施例１と同
様にして、130℃で30分間反応させ、ポリエーテルを得
た。Example 6 260 mg (1.7 mmol) of CaF was weighed into a polymerization tube, dried by heating, and then 7.7 ml of methyl glycidyl ether (85.6 mg).
Mmol), and phenyltrimethylsilyl ether
0.31 ml (1.7 mmol) was added and reacted at 130 ° C. for 30 minutes in the same manner as in Example 1 to obtain 7.5 g of polyether (yield 1).
00%). n = 2440; D = 1.23 Comparative Example 1 A reaction was performed at 130 ° C. for 30 minutes in the same manner as in Example 1 except that cesium phenolate (PhOCs) was used instead of the initiator and the inorganic fluoride catalyst of the present invention. A polyether was obtained.
比較例２ 重合管に、ZnF2177mg（1.71ミリモル）を量り込み、
加熱乾燥した後、ｎ−ブチルグリシジルエーテル12.2ml
（85.6ミリモル）と、フェニルトリメチルシリルエーテ
ル0.31ml（1.71ミリモル）を加え、脱気封管後、130℃
で30分間反応させた。反応後、反応液を濾過してZnF2を
除き、さらにｎ−ブチルグリシジルエーテルを減圧除去
した。その結果、IR及び1H−NMR分析により、ポリエー
テルが生成していないことを確認した。Comparative Example 2 177 mg (1.71 mmol) of ZnF 2 was weighed into a polymerization tube,
After heating and drying, n-butyl glycidyl ether 12.2 ml
(85.6 mmol) and 0.31 ml (1.71 mmol) of phenyltrimethylsilyl ether were added.
For 30 minutes. After the reaction, except ZnF 2 The reaction was filtered and the further n- butyl glycidyl ether was removed under reduced pressure. As a result, it was confirmed by IR and 1 H-NMR analysis that no polyether was generated.
比較例３ 重合管に、KHF2133mg（1.71ミリモル）を量り込み、
加熱乾燥した後、ｎ−ブチルグリシジルエーテル12.2ml
（85.6ミリモル）と、フェニルトリメチルシリルエーテ
ル0.31ml（1.71ミリモル）を加え、脱気封管後、130℃
で30分間反応させた。反応後、反応液を濾過してKHF2を
除き、さらにｎ−ブチルグリシジルエーテルを減圧除去
した。その結果、IR及び1H−NMR分析により、フェニル
トリメチルシリルエーテルに対して、約１当量分のｎ−
ブチルグリシジルエーテルが付加したが、それ以上の反
応の進行がなかったことを確認した。Comparative Example 3 133 mg (1.71 mmol) of KHF 2 was weighed into a polymerization tube.
After heating and drying, n-butyl glycidyl ether 12.2 ml
(85.6 mmol) and 0.31 ml (1.71 mmol) of phenyltrimethylsilyl ether were added.
For 30 minutes. After the reaction, except KHF 2 The reaction was filtered and the further n- butyl glycidyl ether was removed under reduced pressure. As a result, by IR and 1 H-NMR analysis, about 1 equivalent of n-
It was confirmed that butyl glycidyl ether was added, but no further reaction proceeded.
実施例１〜５及び比較例１の反応条件及び生成物のGP
Cの結果を合わせて、第１表に示した（分子量はポリス
チレン換算）。比較例１のフェノキシドアニオンによる
重合例と対照的に、実施例１〜５において分子量分布
（Ｄ）の狭いポリエーテルが得られた。また、その数平
均分子量（ｎ）はモノマーと開始剤（シリルエーテ
ル）との比及び変換率より算出した計算値とよく対応し
ており、容易に分子量制御が可能であった。これらの結
果は本発明の重合系のリビング性を示すものである。Reaction Conditions of Examples 1 to 5 and Comparative Example 1 and GP of Product
The results of C are shown in Table 1 (the molecular weight is in terms of polystyrene). In contrast to the polymerization example using phenoxide anion of Comparative Example 1, polyethers having narrow molecular weight distributions (D) were obtained in Examples 1 to 5. The number average molecular weight (n) well corresponded to the calculated value calculated from the ratio of the monomer to the initiator (silyl ether) and the conversion, and the molecular weight could be easily controlled. These results show the living properties of the polymerization system of the present invention.
第１図は実施例２〜４で得られた反応液より触媒を濾別
し、濾液をテトラヒドロフランに溶解させ、GPC分析を
行った結果を示す。 これらのチャートにおいて、右のピークはエポキシモノ
マーに、左のピークはポリエーテルに基づく溶出曲線を
示す。FIG. 1 shows the results obtained by filtering the catalyst from the reaction solutions obtained in Examples 2 to 4, dissolving the filtrate in tetrahydrofuran, and performing GPC analysis. In these charts, the right peak shows the elution curve based on the epoxy monomer, and the left peak shows the elution curve based on the polyether.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−278529（ＪＰ，Ａ) 特開 平２−29429（ＪＰ，Ａ) 特開 昭47−6994（ＪＰ，Ａ) 特開 昭47−6993（ＪＰ，Ａ) 特開 平２−196825（ＪＰ，Ａ) 特許2620290（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.6，ＤＢ名) C08G 65/00 - 65/48 ＣＡＳＯＮＬＩＮＥ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-278529 (JP, A) JP-A-2-29429 (JP, A) JP-A-47-6994 (JP, A) JP-A-47-699 6993 (JP, A) JP-A-2-196825 (JP, A) Patent 2620290 (JP, B2) (58) Fields investigated (Int. Cl. 6 , DB name) C08G 65/00-65/48 CASSONLINE ( STN)
Claims (1)
基またはアリール基を示す） で示されるシリルエーテル0.01〜0.2当量を開始剤とし
て、CsFの存在下に重合させ、末端にシリルオキシ基を
持つポリエーテルを得ることを特徴とするエポキシ化合
物の重合方法。1. The compound of the general formula (I) (Wherein R represents a substituted or unsubstituted alkyl group) represented by the general formula (II) (Wherein R 1 , R 2 , and R 3 each represent a substituted or unsubstituted alkyl group or an aryl group). The initiator is polymerized in the presence of CsF using 0.01 to 0.2 equivalents of a silyl ether represented by the following formula: A method for polymerizing an epoxy compound, comprising obtaining a polyether having a silyloxy group.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1102375A JP2911911B2 (en) | 1989-04-21 | 1989-04-21 | Epoxy compound polymerization method |
| US07/502,415 US5017684A (en) | 1989-04-21 | 1990-03-30 | Method of polymerizing epoxy compound |
| DE69023535T DE69023535T2 (en) | 1989-04-21 | 1990-04-02 | Process for the polymerization of epoxy compounds. |
| EP90303511A EP0393872B1 (en) | 1989-04-21 | 1990-04-02 | Method of polymerizing epoxy compound |
| AT90303511T ATE130326T1 (en) | 1989-04-21 | 1990-04-02 | METHOD FOR POLYMERIZING EPOXY COMPOUNDS. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1102375A JP2911911B2 (en) | 1989-04-21 | 1989-04-21 | Epoxy compound polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02281030A JPH02281030A (en) | 1990-11-16 |
| JP2911911B2 true JP2911911B2 (en) | 1999-06-28 |
Family
ID=14325715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1102375A Expired - Lifetime JP2911911B2 (en) | 1989-04-21 | 1989-04-21 | Epoxy compound polymerization method |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5017684A (en) |
| EP (1) | EP0393872B1 (en) |
| JP (1) | JP2911911B2 (en) |
| AT (1) | ATE130326T1 (en) |
| DE (1) | DE69023535T2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4943626A (en) * | 1988-07-29 | 1990-07-24 | The Dow Chemical Company | Primary polyether active hydrogen compounds which are prepared from linked, protectively initiated polyalkyleneoxides |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2620290B2 (en) | 1988-03-11 | 1997-06-11 | 旭電化工業株式会社 | Method for producing aryl ether compound having silyloxy group |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3503898A (en) * | 1968-02-16 | 1970-03-31 | Koppers Co Inc | Cationic polymerization catalyst |
| US3660315A (en) * | 1970-09-22 | 1972-05-02 | Du Pont | Process for preparing fluorine-containing polymers |
| US4336366A (en) * | 1980-02-29 | 1982-06-22 | Ciba-Geigy Corporation | Thermally polymerizable mixtures and processes for the thermally-initiated polymerization of cationically polymerizable compounds |
| US4448980A (en) * | 1983-09-22 | 1984-05-15 | E. I. Du Pont De Nemours And Company | Preparation of trialkylsilyl ethers |
| JPH01278529A (en) * | 1988-04-30 | 1989-11-08 | Cemedine Co Ltd | Ring-opening of heterocyclic compound and polymerization thereof |
-
1989
- 1989-04-21 JP JP1102375A patent/JP2911911B2/en not_active Expired - Lifetime
-
1990
- 1990-03-30 US US07/502,415 patent/US5017684A/en not_active Expired - Fee Related
- 1990-04-02 AT AT90303511T patent/ATE130326T1/en not_active IP Right Cessation
- 1990-04-02 DE DE69023535T patent/DE69023535T2/en not_active Expired - Fee Related
- 1990-04-02 EP EP90303511A patent/EP0393872B1/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2620290B2 (en) | 1988-03-11 | 1997-06-11 | 旭電化工業株式会社 | Method for producing aryl ether compound having silyloxy group |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE130326T1 (en) | 1995-12-15 |
| EP0393872B1 (en) | 1995-11-15 |
| DE69023535D1 (en) | 1995-12-21 |
| US5017684A (en) | 1991-05-21 |
| JPH02281030A (en) | 1990-11-16 |
| EP0393872A3 (en) | 1991-08-28 |
| EP0393872A2 (en) | 1990-10-24 |
| DE69023535T2 (en) | 1996-05-30 |
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